Oxirane triazine resinous compositions and processes of preparing the same



United States OXKRAIIE TRIAZENE RESEN JUS CGMPfiSlTIGNS AND PRGCESSEES (BF EREEARDJG THE SAli iE Charles Frazier, Yonkers, N. Y., and Leonard E. Cadwell, Springdale, Cam assignors to American (lyanannd Company, New York, N. Y., a corporation of Maine N Drawing. Application July 1, 1953, Serial No. 365,545

27 Claims. (Cl. 269-455) wherein X represents a halo group, Y represents (a) a member selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, (b) amine radicals represented by the formula NRR where R and R each represents a member having the same meaning as (a), and (c) radicals represented by the formula -OR" wherein R" represents a member selected from the group consisting of alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, and n represents an integer which is at least 1 and not more than 3. More particularly this invention relates to a novel composition of matter comprising the polymer of (1) an alpha, beta unsaturated carboxylic acid, (2) an alizyl ester of an alpha, beta unsaturated carboxylic acid and (3) a polymerizable compound different from (1) and (2) containing a polymerizable CH2=C group, said polymer having an acid number of at least 15, in physical admixture with the dehydrohalogenated reaction product of a monohalohydrin of a saturated aliphatic trihydric alcohol and a compound having the general formula:

wherein X represents a halo group, Y represents (a) a member selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, (b) amine radicals represented by the formula NRR' where R and R each represents a member having the same meaning as (a), and (c) radicals represented by the formula R wherein R" represents a member selected from the group consisting of alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, and n represents an integer which is at least 1 and not more than 3.

One of the objects of the present invention is to produce a composition of matter substantially as described hereinabove. A further object of the present invention is to produce a surface coating composition having excellent mar resistance, excellent chemical resistance, together with outstanding flexibility, color retention and color stability.

atent G 2,810,705 Patented Get. 22, 1957 These and other objects of the present invention will be discussed more fully hereinbelow.

In the preparation of the composition of the present invention, one may react the alpha, beta unsaturated carboxylic acid and different compounds containing the polymerizable CHz=C group, preferably inthe presence of an inert organic solvent and then physically mixed with oxiraue derivatives as described hereinabove. This physical admixture may then be applied as a coating composition by drawing down films therefrom and dried either by air drying or baking to produce a film having all of the desirable properties indicated hereinabove.

The oxirane triazines which are used as a reactant in the practice of the process of the present invention is a polymerizable compound containing both atriazine ring and at least 1 and not more than 3 reactive epoxy groups. These polymerizable oxirane compounds containing at least one oxirane ring and a triazine ring may be obtained by reacting a monohalohydrin of a saturated aliphatic trihydric alcohol wherein the halogen grouping is selected from the group consisting of chlorine, bromine and iodine with a compound represented by the general formula:

N ll 0 wherein X represents a halo group, Y represents (a) a member selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, (b) amine radicals represented by the formula NRR where R and R each represents a member having the same meaning as (a), and (c) radicals represented by the formula --OR" wherein R" represents a member selected from the group consisting of alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, and n represents an integer which is at least 1 and not more than 3 From a consideration of the'above formula it will be noted that when small n is 3 there will be no radicals represented by Y added to the triazine nucleus.

Illustrative examples of hydrocarbon radicals which R, R and R may represent in the above formula are as fol lows: The saturated aliphatic radicals such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, amyl, isohexyl, octyl, decyl, dodecyl, octadecyl and the like, including saturated cycloaliphatic radicals such as cyclopentyl, cyclohexyl, cycloheptyl and aromatic substituted saturated aliphatic groups such as benzyl, phenylethyl, phenylpropyl, phenylisopropyl, etc.; aromatic groups such as phenyl, biphenyl, naphthyl, etc., including saturated aliphatic substituted aromatic groupings e. g. tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, butylphenyl, etc. Illustrative examples of alkenyl radicals which may be employed in the above formula are allyl, methallyl, ethallyl, propallyl Z-butenyl, 3-butenyl, B-methyl-Z-butenyl, 3-methyl-3-butenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, Z-methyl-Z-pentenyl, 3-methyl-4-pentenyl, 2-hexenyl, 3-nonenyl, etc. Examples of compounds embraced by the formula set forth here and above which are reacted with a monohalohydrin of a saturated aliphatic trihydric alcohol to form the reactant (4) here and above are as follows: cyanuric chloride; 2,4-dichloro-1,3,5-triazine; 2,4-dibromo-6-phenyl-1,3,5-triazine; 2,4-dichloro-6- methyl-1,3,5-triazine; 4,6-diio-do-2-alloxy-1,3,5-triazine; 2,4-dichloro-6-methoxy-1,3,5-triazine; 2-amino-4,6-dichloro-1,3,5-triazine; 2-butylarnino-4,6-dibromo-1,3,5-triazine; 2-diallylamino-4,6-dichloro-1,3,5-triazine; 2,4-diamino-6- chloro-1,3,5-triazine; 2-amino-4-bromo-6-methylamino- 1,3,5-triazine; 2-amino-4-iodo-6-o-toluino-1,3,5-triazine; 2 chloro 4 di(n butyl) amino 6 ethylamino 1,3,5

triazine; 2,4 bis (diallylamino) 6 fluoro 1,3,5 triazine; 2 chloro 4 hexylamino 6 phenylethylamino 1,3,5 triazine; 2 amino 4 bromo 6 propyl 1,3,5 triazine; 2 amino 4 chloro 6 propyl 1,3,5 triazine; 2 chloro 4 ethylamino 6, a phenyl 1,3,5 triazine; 2 butyl 4 chloro -'6 propylamino 1,3,5 triazine; 2 bromo 4,6 bis (diallylamino) 1,3,5 triazine; 2

'fluoro 4 methylamino 1,3,5 triazine; 2 amino 4 chloro 1,3,5 triazine; 2 amino 4 chloro 6 phenoxy 1,3,5 triazine; 2 chloro 4 methylamino 6 methoxy 1,3,5 triazine; 2 di(n butyl)amino 4 iodo 6 methoxy 1,3,5 triazine;'2 brorno 4 diethylamino 6 phenoxy 1,3,5 triazine; 2 bromo 4 ethoxy 6 octylamino 1,3,5 triazine; 2 cyclohexylamino 4 'ethoxy 6 iodo, 1,3,5 triazine; 2,4 diethoxy 6 fluoro 1,3,5 triazine; 2 chloro 4,6 dibutoxy 1,3,5 tria'zine; 2 chloro 4,6 diphenoxy 1,3,5 triazine; 2

'bromo 4 phenoxy 1,3,5 triazine; 2,4 diiodo- 6 phenoxy 1,3,5 triazine; 2 fluoro 1,3,5 triazine; 2

chloro 4 decyl 6 -'p tertiary butylphenoxy 1,3,5

' triazine; 2 bromo -,4 phenyl 6 p tertiarybutylphenoxy 1,3,5 triazine; 2 chloro 4,6 dipropyl 1,3,5 triazine;

2 chloro 4 methyl 1,3,5 triazine, and the like. The monohalohydrins of a saturated aliphatic trihydric alcohol that are-used in the reaction with the triazines mentioned hereinabove to prepare the oxiran-e triazines used in the preparation of the product of the present invention are derivatives of a trihydric alcohol such as glycerol, butanetriol-1,2,4; pentan'etriol-1,2,5; hexanetriol-l,2,6 and similar analogs. The halohydrins are distinguished by having at least one primary hydroxyl group and .preferably one primary and one secondary hydroxyl, The halogen atom is preferably substituted on a carbon'atom adjacent to the carbon atom bearing the secondary hydroxyl. The halogens may include chlorine, bromine and iodine. Alpha monochlorohydrin of glycerol (l-chloropropanediol) is the preferred alcohol halide and simple analogsmay'be represented by V OH or HOCHr-UCH( JHZ V where'U, represents alkylene radicals and Z represents hydrogen andaliphatic radicals; Thus, the halohydrins may include 1-chloro-butanediol-2-4; 3-chloro-pentanediol-1,4; etc. Glycerol-beta-mono-chlorohydrin represents a com-' pound where a diprimary hydroxyl bearing monohalohydrin may be utilized in our invention. Other halohydrins that find use in our invention are such as 3-chlorobutanediol-1,2; 2-bromobutanediol-1,3; 1-chloropentanediol-2,5;

3-iodopentanediol-3,5; 1-chlorohexanediol-2,6; 2-bromohexanediol-3,6; 3-chlorohexanediol-l,2 and the like.

In the reaction between'the halotriazine and the mono- 'halohydrin, reaction probably first takes place at the primary hydroxyl position of the latter. In the second stage, thesecondary hydroxyl participates in dehydrohalogenation leading to formation of the oxirane ring. Since the halo group ofthe alcohol is removed from the compound, it is immaterial which halohydrin is used as a starting material from the halo group standpoint.

In order that the present invention may be more completely understood, the following examples are set forth primarily for the purpose of illustration only in which all parts are parts by weight. details set forth in these examples should not be interpreted as limitations on the case except as indicated in the appended claims.

' 'Preparation of triglycidyl cyanarate 184'partsof cyanuric chloride and 331.5 parts of glycerol-alpha-monochlorohydrin were dissolved in 1200 parts of dioxane. 240 parts of dry finely powdered sodiumhydroxide were added to the vigorously stirred dioxane solution over a period of 2 hours. Some external cooling wasnecessai'y to maintain the temperature between 25-35 C. The mixture was stirred for an additional 5 hours at;

, were reacted in 7.5 parts diethyl ether of ethylene glycol V Any specific enumeration of a r 4 about 3035 C. and then filtered. The solid was pressed dry, slurried with 300 parts fresh dioxane at 40 C. and refiltered. The combined filtrates were concentrated under reduced pressure, keeping'the pot temperature below 35 C. to give 550 parts of solution which was 36.5 percent solids.

Preparation of 2glycidyl0xy-4.6-a'imethoxy-1,3,5 triazine Preparation of 2-glycidyl0xy-4,6-diphenoxy-s-triazine 2-chloro-4,6-diphenoxy striazine was prepared according to the method described in J. A. C. S. 73, page 2992 (1951). 30 parts of thesame together with 11 parts glycerol-alpha-monochlorohydrin were dissolved in 75 parts dioxolane and as the mixture was stirred, 8 parts powdered sodium hydroxide were added over a period of about 20 minutes while controlling the temperature at 2530 C.

Following the addition, this temperature was maintained -for an additional hour, then the mixture was filtered. The

solution obtained yielded a water white, resinous film when dried at 70 C.

Preparation of 2-amin0-4 glycidyloxy-6-a'ibutylamino-s- V .triazz'ne 7 1.1 parts of 2-amino-4-chloro-6-phenylamino-s-triazine and 0.55 part of glycerol-alpha-monochlorohydrin were reacted as above with 0.4 part sodium hydroxide using 10 parts dioxane as solvent. The' recovered product was partly crystalline.

Preparation of 2-glycidyloxy-4,6-di(phenylamino)4,3,5-

. triazine 0.75 part of 2-chloro-4,6-di(phenylamino)-1,3,5-triazine and 0.28 part of glycerol-alpha-monochlorohydrin with 0.20 part sodium hydroxide. The product recovered from solution was partly crystalline. When heated, it first melted and then set due to its thermos'etting characteristic.

Preparation of 2,4-diglycidyloxy-6-p-tertiarybutylphenoxys-triazine containing 14.9 parts of the triazine and 11.1 parts ofglycerol-alpha-monochlorohydrin were agitated as 8.0

. parts sodium hydroxide were added. The exothermic reaction was controlled at 20-25 C for hour. The tem-' perature was then raised and held at 50 C. 1 hour. The.

main product isolated in solution form dried at 70 C(to a clear, balsam-like material. This hardened to a clear, slightly brittle film after heating at C. 1 hour- It was then only'slightly swelled by contact with acetone.

tion with pyridine hydrochloride.

cyanuric chloride, phenol and sodium hydroxide by re- "tionat 5 C. and isolated in dry crystalline form. 24 parts together with 22 parts glycerol-alpha-monochloro hydrin were dissolved in 50 parts methyl isobutyl ketone C. The reaction product in solution form was examined ,Bakingat 120 C. for 1 hour was suificient to harden it equal volume of toluene.

Preparation of 2,4-diglycidyloxy-6rphenoxy-s-triazine peratures the removal of the halogens from the triazine compound is not complete and consequently the oxirane yield is low. For'high yields of the oXirane triazines a slow addition of an acceptor for the freed halogen, e. g.,

over a period of l to 2 hours, with a minimum amount of cooling necessary to control the exotherm and an additional reaction time of from about 2 to 5 hours with a preferred time of about 4 hours gives the best results. The solvent employed in the process of our invention is o limited to those which are non-reactive toward the tri- When dned at 70 azine compound, the monohalohydrin of the trihydric alcohol, the oxirane group formed or the'halogen acceptor and must dissolve the reactants and the oxirane containing product. A satisfactory solvent is dioxane.

Other solvents that may find employment in the instant process are acetone, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxolane, dimethyl formamide, methyl isobutyl ketone, dichlorobenzene, etc. From an examination of the formula setting forth the reaction'mechanism, it will be seen that during the dehydrohalogenation HCl, HI, HF or HBr will be formed depending upon the particular halogen present in the 2,4-dichloro-6-phenoxy-s-triazine was prepared from action of equimolecular quantities in acetone water soluazd reacted with 16 parts sodium hydroxide at 2025 for its film forming characteristics. Cathe solution yielded a soft, plastic film free of color.

to a slightly brittle state. Contact with the original solvent then had practically little effect. The solution of the unpolymerized product withstood dilution with an' The reaction involved in preparing the glycidyl derivatives of these triazines is a two-step mechanism. For example, when cyanuric chloride is reacted with glycerolalpha-monochlorohydrin in a suitable solvent under mild heating conditions and with the addition of a suitable HCl acceptor, a chlorohydroxypropyl cyanurate type derivative is first formed. The additional HCl acceptor compound of the general formula and also upon the added to the reaction mix dehydrohalogenates the chlorohalogen PT?Sent ill the mollohalohydrin- As used herein, hydroxy ro yl grou t glycidyl adi l thu fo mi g a halogen acceptor is any compound that will accept or a polymerizable product containing both the oxirane and neutralize the halogen acid formed- The amount of triazine groups. The following formulas et fo th the halogen acceptor introduced into the reaction mixture reaction mechanism: will therefore be determined by the number of halogen N OH /N on C/ \C l (g C/ C-O--CHz-CHCH2CI l I] +HO-CH: H-CHzCl I] N /N N /N \C \C l l /N O C/ C-OCH:C- CHz +1101 l l In the preparation of these triazine derivatives, the atoms freed during the reaction. In order to insure a molar proportion of the monohalohydrin of a saturated complete acceptance or neutralization of the liberated aliphatic trihydric alcohol to the triazine compound rephalogen an excess of halogen acceptor may be introduced resented by the general formula shown above will be into the reaction mass without being detrimental to the determined by the number of halogens present in the desired reaction. Any excess halogen acceptor present latter compound. For example, when cyanuric chloride may be easily separated from the reaction product. Suitis employed, 3 mols of the monohalohydrin of the triable halogen acceptors are such inorganic basic materials hydric alcohol will be used for each mol of cyanuric as sodium hydroxide, calcium oxide, barium oxide, sochloride if it is desired to produce the tri-substituted dium carbonate, potassium hydroxide, sodium bicarbonderivative. When compounds such as 2-chloro-4,6-diate, calcium hydroxide, potassium oxide, barium carbonmethoxy-1,3,5-triazine are employed, 1 mol of the monoate, barium hydroxide, sodium aluminate and the like. halohydrin of a trihyd'ric alcohol will be utilized. Cor- One of the essential reactants in the preparation of respondingly, when a dihalo triazine compound is utilized, the copolymer used in the present invention is a polymeriz- 2 mols of a monohalohydrin of a saturated aliphatic triable compound containing aCHz=C group, which comhydric alcohol will be used per mol of the compound. pound is different from an alpha, beta unsaturated car- It will thus be seen that the molar proportion of monoboxylic acid. Amongst the specific compounds of this halohydrin to halo triazine may vary from about 1:1 to class, which may be used, are the styrenes both ring subabout 3:1 depending upon the particular halo triazine stituted and side chain substituted styrenes as well as reacted and the end product desired. A slight excess of 60 styrene per se. Amongst the side chain substituted stymonohalohydrin may even be used in our invention if renes which may be used are alpha methyl styrene, alpha 'so desired. A molar proportion of less than 1 mol of ethyl styrene, alpha chloro styrene and the like. Amongst monohalohydrin per halogen present in the general forthe ring substituted styrenes which may be used are the mula may also be used. Thus, when cyanuric chloride ortho, meta or para alkyl styrenes such as o-methyl styis reacted with a monohalohydrin, l, 2 or 3 mols of the rene, n-ethyl styrene, p-propyl styrene, or the polyalkyl monohalohydrin may be employed. This variation in styrenes such as 2,4-dimethyl styrene, 2,5-diethyl styrene, the molar proportion of monohalohydrin is also possible 3,4-dimethyl styrene and the like. Other ring substituted when a dihalo compound of the general formula is presstyrenes that may be used are the o, m or p halo styrenes ent. In that instance, 1 or 2 mols of monohalohydrin P such as o-chloro styrene, p-bromo styrene, m-iodo styrene, may be reacted with 1 mol of the dihalo compound. 2,4-dichloro styrene, 2,5-dichloro styrene, 3,4-dibromo sty- The temperature of reaction should be within the range rene and the like. Other halo substituents such as iodo of from about 0 C. to about 75 C. with a range of from and fluoro in these and comparable positions may be about C. to about C. preferred for optimum used. Other alkyl substituents, then, such as those set yield. At elevated temperatures the halogen acceptor forth hereinabove may be substituted on the ring such tends to decompose the oxirane ring, while at low temas isopropyl, butyl, pentyl, hexyl and the like. Illustra- 2,810,706 7 T tive of other 'compounds which may be used are acrylo- I nitrile, 'methacrylonitrile, ethacrylonitrile or the alkyl esters Y of alpha beta"unsaturated carboxylic acids containing a -lpo1yiherizable CH2C group, such as the methyl, ethyl, 7 propyl, butyl, hexyl, octyl ester of acrylic acid, methacrylic 5 acid and the like. Amongst other compounds which may be used in this class are allyl alcohol, allyl acetate, methallyl alcoholfallyl lacta'te, the allyl ester of alpha-hydroxyisobutyric" acid, allyl acrylate, allyl methacrylate, diallyl carbonate, diallyl malonate, diallyl bxalate, diallyl succinate, diallyl gluconatefdiallyl methylgluconate, diallyl between about 95:5 and 60:40, respectively. "It is preferred, however, that the ratio in parts by weight. between these reactants be between about 80:20 and 70:30 "respectivelys 71--. In the practice of the process of the present-invention, one may charge the alpha, beta unsaturated carboxylic 7 acid, the, CH2=C type compound with. or withdtitthe alkyl ester of the alpha, beta unsaturated carboxyliciacid to a suitable reaction vessel, and reacted to 'fo'fmfthe polymer having an acid number-of at least and'thereafter mixing the polymer with the oxirane triazine.de-

- adipate, the'diallyl ester of azelaic acid, diallyl sebacate, diallyl tartronate, diallyl tartrate,diallyl silicone, diallyl silicate, diallyl fuinarate, diallyl maleate, diallyl mesaconatejdiallyl citraconate, diallyl 'glutaconate, the diallyl ester 'of muconic acid,'diallyl itaconate, diallyl phthalate, the-diallyl ester 'ofer'idome'thylene tetrahydrophthalic anhydride, triallyl tricarballylate, triallyl aconitate, triallyl i citrate,"triallyl phosphate, trimethallyl phosphate, the diallyl. ester 'of ethylene glycol dicarbonate, the diallyl esterloffethyleneglycol dimalonate, the diallyl ester of f ethylene glycol dioxalate, the diallyl ester of diethylene Y glycol dicarbonate, .the diallyl ester of diethylene glycol -dimalonate; theidiallyl ester of diethylene glycol dioxalate, the diallyl ester of carbonic acid or ,of other dicarboxylic acids, diesters of otherglycols, e. g., pro :pylene glycol, the butylene glycols, triethylene glycol,

etc., tetraallyl silicate and other tetraallyl esters.

The alpha, beta unsaturated carboxylic acids which may be used in the preparation of the polymers of the present invention may be either the monoearboxylic' acids or the polycarboxylic acids, but it is necessary that the unsaturation in these acids be between the alpha,

beta carbon atoms. Amongst those acids which may be used are acrylic acid, crotonic acid, isocrotonic acid, meth-' acrylic, fumaric, maleic, glutaconic, citraconic, itaconic,

and the like. Whenever available, the anhydridesof these acids may be used and furthermore mixtures of these acids or their anhydrides may be used in the prepartion of the products of the present invention. When the anhydrides are used, not more than 1 ethylenically unzsaturated double bond should be present in the anhydride. The'acidcomponent o f'the'reaction product designated sometimes in this case as (1) should be used in an amount sufiicient so that the reaction product of the alpha, beta unsaturated'carboxylic acid, the CH2=C material with or without the alkyl ester of the alpha, beta unsaturated carboxylic acid has an acid number of at least about 15 and preferably between about 25 and 100. It is of course possible;to have a polymer which has an acid number substantially in excess of 100 such as an acid number of 500.

The third reactant to thepolymerization process is not imperative but is preferred and is identified sometimes in this case as (2) namely an alkyl ester of an alpha, beta unsaturated carboxylic acid. Included in that group would be alkyl esters such 'as the methyl, ethyl, propyLdsopropyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, lauryl; octadecyl esters of such acids. as acrylic acid, crotonic acid, isocrotonic acid, methacrylic acid, fumaric acid, maleic acid, glutaconic acid, citraconic acid, itaconic acid, and the like. The amount of the alkylester of the alpha, beta unsaturated carboxylic acid' present in the preferred reaction mixture will depend on the amount of the polymeriz able CH2=C group type compound which is present. The ratio between the CH2=C type compound and the alkyl ester of the alpha, beta unsaturated carboxylic acid should be not less than about 1:1, 7

respectively, and not greater than about 6:1 CH2=C group compound toester, respectively. Preferably one would use a mol ratio of between about 2:1 and 4:1 with an optimum being observed at a mol ratio of 3: 1. V

The weight ratio between the polymer of (l) and (2) or. 1), (2). and (3) and the oxirane triazine compound may be varied over a ifairlyfsubstantial range such as rivative to produce the composition of the present invention. 'In order that the present invention maybe i more completelyunderstood, the following examples are set forth in which all parts are parts by Weight. These examples are set forth primarily for therpurpose of illustration and any specific enumeration of .detail:contained therein should notbe interpreted as a limitation on the case except as is indicated in the appended claims.

7 EXAMPLE 1' 50 parts of amyl acetate is introduced into a suitable reaction vessel equipped with thermometer, stirrer and reflux condenser. 'The acetate is heated to the reflux temperature whereupon a mixture of 9.6 parts of glacial acrylic acid, 28-.7 parts 'of styrene, 11.7 parts of butyl acrylate and 1 .0 part of cumene hydroperoxide are added V sistance and good alkaliresistanee. p u 7 A comparable film was'drawndown from a' composito the refluxing acetate in small quantities over'a period of about one hour. When the addition of the mixture is complete the reaction mixture is refluxed for an ad- 2 ditional 5 hours. The viscosity is Z4 plus. on the Gardner- Holdt scale;at25 CJand 'ata'n' acidnumber of 149.5. A mixture of 60 parts of the copolymer thus prepared and 40 parts of glycidyl cyanurate is prepared and, a film is drawn down on a steel panel and baked for 30 minutes at 300 F. The film thus produced had good mar retion comprising parts of the copolymer prepared as indicated hereinabove in a mixture with 40 parts of diglycidyl phthalate and baked for 30 minutes at 300 F. This film proved to be not mar resistant at all and had very poor alkali'resistance'and was poorly resistant to amyl acetate: 1 a

A comparable film was drawn down from the copolymer alone as prepared hereinabove and the for 30 minutes at 300 F. was not mar resistant, was very brittle and had poor resistance to amyl acetate. 9

A comparable film was drawn down under the same conditions from glycidyl cyanurate alone and the film was hard, but brittle and displayed poor alkali resistance.w

EXAMPLE 2 48 parts of acrylic acid, 423 parts of butyl acrylate, 1029 parts of styrene and 1500 parts amyl acetate are introduced into a suitable reaction chamber and refluxed for about 5 hours in the presence of 30 parts of cumene hydroperoxide. The acid number, of the resulting polymer was 25, the viscosity was S on the Gardner- Holdt scale at 25 C., the color was. 1 (Gardner-Holdt) and the appearance was clear. parts of the'copolymer solids thus prepared and 30 parts of triglycidyl cyanurate are blended and-a film is drawn down and is baked for 30 minutes at 300 F. Y The film displayed enhanced mar resistance and good alkali resistance.

' EXAMPLE 3 fihn after baking solution was clear. 70 parts of the copolymer solids and 30 parts of triglycidyl cyanurate are blended together and a film is drawn down which is baked for '30 minutes .at 300 F. The resulting filmwas clear, had an excellent mar resistance and very good resistance to solvents such as alkalis and amyl acetate.

EXAMPLE 4 192 parts of acrylicacid, 381 parts of butylacrylate, 927 parts of styrene, 1500 parts of amyl acetate and 30 parts of cumene hydroperoxide are introduced into a suitable reaction vessel comparable to that used in Example 1 and the mixture is heated at about the reflux temperature for hours. The resulting copolymer solution had an acid number of'lO0, a viscosity of Y on the Gardner-Holdt scale and a color of 1 (Gardner-Holdt). The appearance of the solution was clear.

A 70:30 mixture of 'this copolymer and triglycidyl cyanurate is prepared anda film is drawn down from this solution and is bakedfor about 30 minutes at 300 F. The resultant film-is clear, had excellent'mar resistance and excellent solvent resistance.

Examples 2, 3 and 4 are repeated except in the place of the amyl acetate the solvent used was methyl Cellosolve. In each instance theacid number again was 25, 50 and 100, respectively, the viscosities were Y-Z, Z /3bubble, and Z l-% bubble, respectively. Each of these copolymers displayed a slight haze'in the solution. When films are drawn down from a mixture of the copolymers in a 70:30 ratio with triglycidyl cyanurate and baked for 30 minutes at 300 F.excellent mar resistance and good to excellent solvent resistance was noted in each instance.

EXAMPLE 5 64 parts of glacial acrylic acid, 309 parts of styrene and 127 parts of butyl acrylate together with parts of cumene hydroperoxide are added to 500 parts of refluxing methyl Cellosolve in comparatively small increments over a 1 hour period. The refluxing is continued for an additional 5 hours. The acid number of the ultimate copolymer is 100.6; the solids content is 48.6 and the conversion of monomer to polymer is 98.2 percent. The color (Gardner-1933) is 1. A 70:30 mixture of this copolymer and triglycidyl cyanurate is prepared and was evaluated as a white baking enamel which had a better curing cycle, chemical resistance and overbake than a commercially available enamel.

EXAMPLE 6 500 parts of methyl Cellosolve are introduced into a suitable reaction chamber equipped as in Example 1 and heated to reflux temperature. While maintaining the methyl Cellosolve at reflux, there is charged thereto a mixture of 32 parts of glacial acrylic acid, 332 parts of styrene, 136 of butyl acrylate, and 10 parts of cumene hydroperoxide. The mixture is added in comparatively small increments over a 1 hour period while being maintained at reflux and upon the completion of the addition, the reaction mixture is refluxed for an additional 5 hours. The viscosity of the copolymer solution was YZ on the Gardner-Holdt scale at 25 C., the acid number 54.4, the solids in the solution were 47.5 percent and the conversion from monomers to polymer was 96.0 percent. The color of the copolymer solution was 1. A mixture of 70 parts of the copolymer solids and 30 parts of triglycidyl cyanurate were prepared as a white baking enamel and films were drawn down therefrom, which were then baked at 300 F. for 30 minutes. This film thus produced had better chemical resistance, better mar resistance and better flexibility and toughness than a standard commercial baking enamel. Still further, it was improved in its curing cycle and overbake.

EXAMPLE 7 1000 parts of a 50/50 mixture of xylol and butanol are introduced into a suitable reaction chamber equippedas in Example 1 and the mixture is heated to refluxtemperature whereupon a mixture of 87 parts of maleic anhydride, 780 parts of styrene and 133 parts of acrylonitrile containing 20 parts of cumene hydroperoxide are introduced in small increments into the refluxing solvent over about a 1 hour period. The reaction is then continued until polymerization is substantially complete. The appearance of the solution is slightly cloudy and the viscosity on the Gardner-Holdt scale at 25 C. is Z5-Z6. A mixture is prepared comprising 70 parts (solids) of the copolymer thus prepared and 30 parts of triglycidyl cyanurate and a film is drawn down on glass using a '4 mil blade and the film is baked for 30 minutes at 300 F. The film thus produced is mar resistant, has a slight haze but has excellent adhesion and toughness.

EXAMPLE 8 Into a suitable reaction vessel equipped as in Example 1 there is introduced 1000 parts of a 50/50 mixture of xylol and butanol. The mixture is heated at the reflux temperature whereupon a mixture of 128 parts of glacial acrylic acid, 745 parts of styrene, 127 parts of acrylonitrile and 20 parts of cumene hydroperoxide are added in small increments, over about a 1 hour period. When the addition is complete, the refluxing is continued until a polymer having an acid number of about is produced. The resulting polymeric solution is clear and has a viscosity of Z6 on the Gardner-Holdt scale at 25 C. A mixture of 70 parts (solids) of the polymer thus prepared and 30 parts of triglycidyl cyanurate is prepared and films are drawn down on glass using a 4 mil blade which are then baked at 300 F. for 30 minutes. The resulting films are clear, have excellent mar resistance, adhesion and toughness.

Amongst the oxirane triazine compounds which may be used as one of the reactants in the practice of the process of the present invention are such compounds 'as:

Triglycidyl cyanurate, 2,4, diglycidyloxy-6-chloro, 1,3;5

triazine 2-glycidyloxy-4,6,dichloro-1,-1,3,5-triazine 2,4 diglycidyloxy-l,3,5-triazine 2,4-diglycidyloxy-6-phenyl-1,3,5-triazine 2,4-diglycidyloxy-6-methyl-1,3,S-triazine 4,6,diglycidyloxy-2-alloxy-1,3,5-triazine 2,4,-dialloxy-6-glycidyloxy-1,3,5-triazine 2,4- diglycidyloxy-6-methoxy-l,3,5-triazine 2-amjno-4,6-diglycidyloxy-l ,3 ,5 -triazine 2-butylamino-4,6, diglycidyloxy-l,3,5triazine 2-diallylamino-4,6-diglycidyloxy-1,3,5-triazine 2,4-diamino-6-glycidyloxy-1,3,5-triazine 2-amino-4-glycidyloxy-6-methylamino-1,3,5-triazine 2-glycidyloxy-4-di (n-butyl) amino-6-ethylamino1,3,5

triazine 2,4-bis (diallylamino)-6-glycidyloxy-1,3,5-triazine 2 glycidyloxy-4-hexylamino-6-phenylethylamino 1,3,5-

triazine 2-amino-4-glycidyloxy-6-propyl-1,3,5-triazine 2-amino-4-glycidyloxy-6-propyl-1,3,5-triazine 2-glycidyloxy-4-ethylamino-6-phenyl-l,3,5-triazine 2-butyl-4-glycidyloxy-6-propylamino-1,3,S-triazine 2-glycidyloxy-4,6-bis(diallylamino)-l,3,5-triazine Z-glycidyloxy-4-methylamino-1,3,5-triazine 2-amino-4-glycidyloxy-1,3,5-triazine 2-amino-4-glycidyloxy-6-phenoxy-1,3,5-triazine 2-glycidyloxy-4-methylamino-6-methoxy-l ,3 ,5 -triazine 2-di(n-butyl)amino-4-glycidyloxy 6 methoxy 1,3,5-

triazine 2-glycidyloxy=4-diethylamino-6-phenoxy-1,3,5-triazine 2 glycidyloxy 4 ethoxy 6 octylamino 1,3,5-triazine 2 cyclohexylamino 4 ethoxy 6 glycidyloxy 1,3,5-

triazine 2,4-diethoxy-G-glycidyloxy-1,3,5-triazine 2-glycidyloxy 4,G-diphenoxy-1,3,5-triazine 2-glycidyloxy-4-phenoxy-1,3,5-triazine 2,4-diglycidyloxy-6-phenoxy-1,3;5triazine 'the' fgroup consisting of alkyl, alkenyl, aryl, alkaryl and kglycidyloxyel,3,5-triazine',- f I; 1' aralkylradicalsfand n represents an integer which is at 2j gly cidyl.bxy '-I4l.rdec'y1.1- of; tertiary butylphehoxyf .leastfl and? not more than 3, wherein the halo group of -l,3,5-triazine A i l tsaid monohalohydrin is -a member selected from the l 2 -glycidyloxy 4 pheny1- 6 5 pitertiaiy butylphenbxy- 5 "g'r'ou'p co'nsisting of chloro, bromo tandriodo, wherein the 1,3,5-triazine t N I t If .f Q 'lt amount (1) added is sufficient to give copolymer of (l'), 2-glycidyloxy-4,6-diptopyl-l,3,5etria2iner11 I (2) and (3) an acid number of at least 15, wherein the 2'-glycidyloxy'-4-methyl-1,3,S-triaZine f. If 1 2eglycidyloxye4-chloro-1,3,5-tria2ii1e.r; tr r wherein the weight ratio of the copolymer of (1), (2) 2-glycidyloxy-4 bromo;6-phenyl-1,3,5;triazine T e 10 and (3) to (4)-is between about 95:5 and 60:40. 12-glycidyloxy-4-chloro-6-methyl-1,3,5etriazine a 2.: Acprocess comprising heat reacting the copolymer "'4-glycidyloxy-6-iodo:2:alloxyel,3,5 triazine ,L 1 Ii .-f' 7 .er (l)-ac ry lic acid; (2) styrene, (3) butyl acrylate with '2-glycidyloxy-4-chloro-6-methoxy-1,3,5-triazine 1 (4) aglycidyl cyanurate, in the presence of an inert or- 2-amino-4-chloro-6-glycidyloxy 1,3,5-triazine 'I 1 I? glganic solventrwhe rein s aidcopolymer has an acid number z-butylamino t-bromo-6-glycidyloxy-1,3,5-triazine- A e of at leas'tvl5-,- th e moi ratio of (2):(3) is between-1:1

2 diallylamino 4 chloro 5 glycidyloxy 1,3,5- to 6:1 and the weight ratio of (1), (2) and (3) to (4) -is triazine, and the like. e between about 95:5 and 60:40; V I

3. A process comprising heat reacting-the copolymer of mol ratio of (2):(3) is between about 1:1 and 1:6, and

tee Prepai'afiee of the eepelymersv of the Present (1) acrylic acid, (2) butyl acrylate and (3) styrene in e invention one may operate witheut benefit of a solvent an inert organic solvent, said copolymer having an acid {medium although it is Preferred that an inertrorganie number of at least 15, with- (4) triglycidyl cyanurate splvent such the ahphatlc or aromane Solvents wherein the mol ratio of (2) :(3) is between about 1:1

' t The a solvents -f may be used are and 1:6, and wherein the weight ratio ofjthe copolymer 3 3 and the one mayuse, ad? a of 1 2 and 3 r (4 is between about 95:5 and ditlonally, mineral splrrts such as Varsol #1, Varsol #2, 60:40 a kerosene and the hke. Additionally, one may make use 4. A process c'omprising heatrreasfing the copolymer of -of such solvents as butyl acetate, amyl acetate, b enzyl (1) an alpha, beta ethylenically unsaturated carboxylic 1 benzyl ether of ethylene glycol mono butyl acid, (2) an alkyl ester of an alpha, beta ethylenically unether of ethylene glycol, 'Carbltol' (monoethyl ether of 4 saturated carboxylic acid and (3) a polymerizable cog? diethylene glycol) methyl cellosolve (monomethyl ether bund containin a t e a e g a CH2 C group and is different from of ethylene glyeoneethyleeueselve (monoethyl ether, of 1) and (2) in an inert organic solvent, with (4) the d eethylene glycol), ethyl, cellqsclve acetate and, Ihe hydrohalogenated reaction product 0f a monohalohyd rin fi 2'5; gf g ggfi gieeg gfi g gz i g $522 ig fg of a saturated aliplhgztic tri'hydric alcohol and a compound viscosity of the polymer solution ultimately desired and 3 havme the eeeera 9 can be varied overave'ry widerange, V7 a 1 I In the preparation of' the eopolymers used intthe present invention, it is generally desired that'a catalyst be p v f employed for the "polymerization reaction; Anyof the t t f" C C v a. a conventional polymerization catalysts may be used in this 4 1 1 connection. Representative members 'of the group of r catalysts are benzoyl peroxide; tertiary butyl hydroper- Wherem X repreeenfie a hale P. refiresente e i oxide, ditertiary butyl peroxide, 2,2 bis(tertiarybutyl perber selected from t e'greup ee e e e (a) a e oxy) butane, cumene hydroperoxide, methyl ethylketone selected f the greup eenslstmg eh e e peroxide, diethyl ketone peroxide and; the like; .The e ary alkeryl arelkyl ei f (e amlee amounts of catalysts employed will be within ,conventionreeleele represented ey'me wi R Whele and al' amounts such as between about 0.0l pereent 'and' 10 R each represent. a member having the same meaning percent by weight based on the total'weigh't of poly'rneri'z- W ,e radicals represented the formula OR able materials present; "Preferably'on'e would "use .be- F P R represents a member reelected from the tween about 0.1 percent and 3' percent by weight, same L eenslstmg of alkyl alkenyl. aryl alkafyl e aralkyl Iedl' basis a I t a t r a cals, and'n represents an integer WhlCh 1s at least land We claim: a t 7 not more than 3, whereln the halo group of said mono- 1. A process comprisingheat reacting the'copolymer h a19hYdIm 1s amember seleeted e g 9- of (1) an alpha, beta ethylenically unsaturated fca'rboxylic slstmg of e lode wherem the amount acid, (2) analk-yl ester of an alpha, beta ethylenically un- (1) added. 15 Sufiielent to glve eepelymer of t e saturated carboxylic acid and (3) a polymerizable 'com- (3) an r number between zs'end wherem the pound containing a group diflfrentffrdmfu) mol ratio of (2 ):(3) 1s between about 1:1 and 1:6, and and (2) in tan inert organic solvent, with (4) the de- ,Whereln thwelght ratlO f he copolymerof (1), (2) and hydrohalogenated reaction product of amonohalohydrin (3) 1(4) 15 between about 95511 :40- i of a saturated an e l h 1 d u d 5. A process comprising heat reacting the copolymer p he ydnc e c e e e p n ,of 1) an alpha, beta ethylenically unsaturated carboxylic h v th e a v a me 6 general, formulta actd, (2) an alkyl ester of an alpha, beta ethylenically un- I V I v a v a saturated carboxylic acid and (3) a polymerizable com- 7 pound containing a CH2=C group and different from e (1) and (2) in an inert organic solvent, with (4) the deh r t 55 hydrohalogenated reaction product of a monohalohydrin V L/ \J r t of a saturated aliphatic trihydric alcohol and a compound having the general formula: H

wherein Xrepresents, a halo group, Y represents a mema ber selected from the group consisting of (a) a member selected from-the group consisting of hydrogen, 'alkyl, N alkenyl, aryl, alkaryl and aralkyl radicals, (l2)- arnine r LA radicals represented vbythe formula NRR' where R L N l and R each represents a member having the same rnean ing as (a), and (c) radicals represented byithetogula qj wherein X represents'a halo group, Y, represents a mem- =OR whrein k 'repres'en'tsa member selected from her selected from the group consisting of (a) a member selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, (b) amine radicals represented by the formula -NRR' where R and R each represents a member having the same meaning as (a), and (c) radicals represented by the formula OR" wherein R" represents a member selected from the group consisting of alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, and n represents an integer which is at least 1 and not more than 3, wherein the halo group of said monohalohydrin is a member selected from the group consisting of chloro, bromo and iodo, wherein the amount of (1) added to form the copolymer is sufiicient to give a copolymer of (1), (2) and (3) an acid number of between 25 and 100, wherein the mol ratio of (2) (3) is between about 1:2 and 1:4, wherein the weight ratio of (1), (2) and (3) to (4) -is between about 80:20 and 70:30.

6. A process comprising heat reacting the copolymer of (1) acrylic acid, (2) butyl acrylate and (3) styrene in an inert organic solvent, said copolymer having an acid number between about 25 and 100, with (4) triglycidyl cyanurate, wherein the mol ratio of (2):(3) is between about 1:2 and 1:4 and wherein the weight ratio of (1), (2) and (3) to (4) is between about 80:20 and 70:30.

7. A composition of matter comprising the reaction mixture of (A) a copolymer of (1) an alpha, beta ethylenically unsaturated carboxylic acid, (2) an alkyl ester of an alpha, beta ethylenically unsaturated carboxylic acid and (3) a polymerizable compound containing a CH2=C group and different from (1) and (2) with (B) the dehydrohalogenated reaction product of a monohalohydrin of a saturated aliphatic trihydric alcohol and a compound having the general formula:

wherein X represents a halo group, Y represents a member selected from the group consisting of (a) a member selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, (b) amine radicals represented by the formula --NRR where R and R each represents a member having the same meaning as (a), and (c) radicals represented by the formula -OR" wherein R" represents a member selected from the group consisting of alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, and n represents an integer which is at least 1 and not more than 3, wherein the halo group of said monohalohydrin is a member selected from the group consisting of chloro, bromo and iodo, dispersed in an inert organic solvent wherein said copolymer has an acid number of at least 15, the mol ratio of (2) :(3) is between about 1:1 and 1:6 respectively, and the weight ratio of (A) to (B) is between about 95:5 and 60:40.

8. A composition of matter comprising the reaction product of (A) a copolymer of (1) acrylic acid, (2) butyl acrylate and (3) styrene and (B) triglycidyl cyanurate in an inert organic solvent wherein said copolymer has an acid number of at least 15, the mol ratio of (2):(3) is between about 1:1 and 1:6 respectively, and the weight ration of (A) to (B) is between about 95:5 and 60:40.

9. A composition of matter comprising the reaction product of (A) a copolymer of (1) maleic anhydride, (2) butyl methacrylate and (3) 2,4-dimethyl styrene, and (B) triglycidyl cyanurate in an inert organic solvent wherein said copolymer has an acid number of at least 15, the mol ratio of (2):(3) is between about 1:1 and 1:6 respectively, and the weight ratio of (A) to (B) is between about 95:5 and 60:40.

10. A composition of matter comprising the reaction product of (A) a copolymer of (1) an alpha, beta ethylenically unsaturated carboxylic acid, (2) an alkyl ester of an alpha, beta ethylenically unsaturated carboXylic acid '24 and (3) a polymerizable compound containing a CH2=C group and different from (1) and (2) with (B) the dehydrohalogenated reaction product of a monohalohydrin of a saturated aliphatic trihydric alcohol and a compound having the general formula:

wherein X represents a halo group, Y represents a member selected from the group consisting of (a) a member selected from the group consisting of hydrogen, alkyl, alkenyl; aryl, alkaryl and aralkyl radicals, (b) amine radicals represented by the formula -NRR where R and R each represents a member having the same meaning as (a), and (c) radicals represented by the formula OR wherein R represents a member selected from the group consisting of alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, and n represents an integer which is at least 1 and not more than 3, wherein the halo group of said monohalohydrin is a member selected from the group consisting of chloro, bromo and iodo, wherein the acid number of said copolymer is at least 15, wherein the mol ratio of (2):(3) is between 1:1 and 1:6 and the weight ratio of (A) to (B) is between about 95:5 and 60:40.

11. A composition of matter comprising the reaction product of (A) a copolymer of (1) an alpha, beta ethylenically unsaturated carboxylic acid, (2) an alkyl ester of an alpha, beta ethylenically unsaturated carboxylic acid and (3) a polymerizable compound containing a CH2=C group different from (1) and (2) with (B) the dehydrohalogenated reaction product of a monohalohydrin of a saturated aliphatic trihydric alcohol and a compound having the general formula:

wherein X represents a halo group, Y represents a member selected from the group consisting of (a) a member selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkaryl and arallryl radicals, (b) amine radicals represented by the formula NRR where R and R each represents a member having the same meaning as (a), and (c) radicals represented by the formula OR" wherein R" represents a member selected from the group consisting of alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, and n represents an integer which is at least 1 and not more than 3, wherein the halo group of said monohalohydrin is a member selected from the group consisting of chloro, bromo and iodo, wherein the acid number of said copolymer is between 25 and 100, wherein the mol ratio of (2):(3) is between about 1:2 and .114 and the weight ratio of (A) to (B) is between about :20 and 70:30.

12. A composition of matter comprising the reaction product of (A) a copolymer of (1) acrylic acid, (2) butyl acrylate and (3) styrene with (B) triglycidyl cyanurate wherein the acid number of said copolymer is at least 15, wherein the mol ratio of (2):(3) is between about 1:1 and 1:6 and the weight ratio of (A) to (B) is between about :5 and 60:40.

13. A composition of matter comprising the reaction product of (A) a copolymer of (1) acrylic acid, (2) butyl acrylate and (3) styrene with (B) triglycidyl cyanurate wherein the acid number of said copolymer is between 25 and 100, wherein the mol ratio of (2):(3) is between about 1:2 and 1:4 and the weight ratio of (A) to (B) is between about 80:20 and 70:30.

14. A composition of matter comprising the reaction product of (A) a copolymer of (1) maleic anhydride, (2)

r as '(a),

r a -OR wherein R" represents a member selected from the is between about 95:5 and 60:40. a a a v 18. A process comprising heat reacting the copolymer of a butyl methacrylate and (3) 2,4-dimethyl styrene with (B) triglycidyl cyanurate wherein the acid number of said copolymer is at least 15, wherein the mol ratio of (2)2(3) is between about 1:1 and '1:6 and the weight ratio of (A) to (B) is between about 95:5 and 60:40.

15. A composition of matter comprising the reaction product of (A) a copolymer of (1) maleic anhydride, (2) butyl methacrylate and 3) 2,4-dimethyl styrene with (B) triglycidyl cyanurate wherein the acid number of f;

said copolymer is between and 100, wherein the mol ratio of (2):(3) is'between about 1:2,and 1:4 and the weight ratio of (A) to (B) is between about 80:20 and 70:30.

acidand (2) adifi erent polymerizable compound containing 21' CHz'="C 'group"in a'n inert organic solvent,

16. A process comprising heat reacting the copolymer of (1) an alpha, beta ethylenically unsaturated carboxylic acid and (2) a diflFerent polymerizable compound containing a CH2=C group in an inert organic solvent,

with (3) the dehydrohalogenated reaction product ofa monohalohydrin of a saturated trihydric alcohol and a compound having the general formula k a i alkenyl, aryl, alkaryl and aralkyl radicals, (b) amine radicals represented by the formula ,NRR' where R and R each represents a member having the same meauing and (c) radicals represented by the formula selected from the group consisting of hydrogen, alkyl,

OR wherein R" representsa member selected fromiithe group consisting of alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, andtn represents an integer which is at least 1 and not more than}, wherein the halo group of said monohalohydrin isa member selected from the group consisting of chloro, bromo and iodo, wherein the amount 1) added is suflicientto give copolymer of 1) and (2) an acid number of at least 15," and wherein the weight ratio of the copolymer of 1) and,(2) to (3) is between i about 95:5 and 60:40.

17. A process comprisingheat'reacting'the copolymer 7 of 1) an alpha, beta ethylenically unsaturated carboxylic acid and (2).a different polymerizable compound containing a CH2=IC group in an inert organiesolvent, with (3) the dehydrohalogenated reaction product of a monohalohydrin of a saturated trihydric alcohol and a compound having the general formula:

wherein X represents a halo group, Y'represents a member selected from the group consisting of (a) a member selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkaryl and aralkyl radicals,i(b) amine radicals represented by the formula 'NRR-where R and R each represents a member having the same'meaning and (c) radicals represented-by the formula consisting of chloro, bromo and iodo, wherein the amount (1) added is sufiicient to givetthe copolymer of (1) and (2) an acid'number of between 25 and 100, and wherein the weight ratio of the copolymer of l) and (2) to (3) (1) an alpha, beta ethylenically unsaturated carboxylic compound having the generalformula;

with (3) the dehydrohaloge'na ted reaction product of a monohalohydrin of a saturated trihydric alcohol and a N whereinX represents a halo group, X represents, a member selected from the group consisting of (a) a member selected-[from the group 'con sistingot hydrogen, alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, (b) amine radicals represented by th e formula ;NRR where Rand R each represents a member having the same meaning as (a), and (c) radicals represented by the formula OR" wherein R represents a member selected from the group consisting of alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, and In represents an integer which is at least 1 and notmore than wherein thethalo group of said t .o o. i

WhereinX represents a halo grounfY represents a member selected from the group consisting ofl (a),a member selected from the group.- consisting of hydrogen, alkyl, alkenyl, aryl, alkaryl an'dja'r'alkyl radicals,- (b), amine radicals represented b'ythe formula r NR R'-where R and R each represents a member having the same meaning as (a), and 1 (c) radic'als represented .by the formula OR wherein R". represents a member selected from the group consisting of alkyl, alkenyl, aryl, alkaryl and aralkyl' radicals, and n represents an integer which is at; least 1 and notmore than 3, whereintthe halo group oflsaid monohalohydrin is a member selected from the group consisting of chloro, bromo and iodo, wherein the amount of (1) in-the copolymer is sutficient to give anacid number of between about 25 and 100, and wherein the weight ratio of (l) a nd-(2) to (3) is between about 80:20 and wherein X represents a halogroun'Y represents amern- :ber select'ed from-the group consisting of (a) a member selected from the group consisting of hydrogen, alkyl,

20. A processZcomprising'heatireactiug the copolymer of (1) an alpha, beta ethylenicallyunsaturated carboXylic acid and (2) a different polymerizable compound having a CH2=C group in an inertorganic solvent, with (3) the dehydrohalogenatedreaction product of a monohalohydrin of a saturated trihydric'alcohol and a compound having the general formula: r

alkenyl, aryl, alkaryl and, aralkyl radicals, (b) amine radicals represented by the formula -NRR where R and R each represents a member having the same meaning as (a), and (c) radicals represented by the formula OR wherein R represents a member selected from the group consisting of alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, and n represents an integer which is at least 1 and not more than 3, wherein the halo group of said monohalohydrin is a member selected from the group consisting of chloro, bromo and iodo, wherein the amount of (1) in the copolymer is sufiicient to give an acid number of 25, wherein the weight ratio of (1) and (2) to (3) is 75:25.

21. A composition of matter comprising a mixture of (A) the reaction product of (1) an alpha, beta ethylenically unsaturated carboxylic acid and (2) a different polymerizable compound containing a CH2=C group and (B) the dehydrohalogenated reaction product of a monohalohydrin of a saturated trihydric alcohol and a compound having the general formula:

wherein X represents a halo group, Y represents a member selected from the group consisting of (a) a member selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, (b) amine radicals represented by the formula NRR where R and R each represents a member having the same meaning as (a), and (c) radicals represented by the formula OR wherein R represents a member selected from the group consisting of alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, and n represents an integer which is at least 1 and not more than 3, wherein the halo group of said monohalohydrin is a member selected from the group consisting of chloro, bromo and iodo, dispersed in an inert organic solvent wherein the copolymer has an acid number of at least and the weight ratio of (A) to (B) is between about 95:5 and 60:40.

22. A composition of matter comprising a mixture of (A) a copolymer of (1) an alpha, beta ethylenically unsaturated carboxylic acid and (2) a diiferent polymerizable compound containing a CH2=C group and (B) the dehydrohalogenated reaction product of a monohalohydrin of a saturated trihydric alcohol and a compound having the general formula:

wherein X represents a halo group, Y represents a member selected from the group consisting of (a) a member selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, (b) amine radicals represented by the formula NRR' where R and R each represents a member having the same meaning as (a), and (c) radicals represented by the formula OR" wherein R" represents a member selected from the group consisting of alkyl, alkenyl, aryl, alkaryl and aralkyl radicals, and n represents an integer which is at least 1 and not more than 3, wherein the halo group of wherein X represents a halo group, Y represents a member selected from the group consisting of (a) a member selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkaryl' and aralkyl radicals, (b) amine radicals represented by the formula NRR' where R and R each represents a member having the same meaning as (a), and (c) radicals represented by the formula OR" wherein R" represents a member selected from the group consisting of alkyl, alkenyi, aryl, alkaryl and aralkyl radicals, and n represents an integer which is at least 1 and not more than 3, wherein the halo group of said monohalohydrin is a member selected from the group consisting of chloro, bromo and iodo, wherein said copolymer has an acid number of 25, and wherein the weight ratio of (A) to (B) is :25.

24. A composition of matter comprising a mixture of (A) a copolymer of methacrylic acid and styrene, said copolymer having an acid number of at least 15 and (B) triglycidyl cyanurate wherein the weight ratio of (A) to (B) is between about 95:5 and 60:40.

25. A composition of matter comprising a mixture of (A) a copolymer of acrylic acid and styrene, said copolymer having an acid number of at least 15 and (B) triglycidyl cyanurate wherein the weight ratio of (A) to (B) is between about 95 :5 and 60:40.

26. A composition of matter comprising a mixture of (A) a copolymer of (1) methacrylic acid, (2) butyl methacrylate and (3) styrene and (B) triglycidyl cyanurate wherein said copolymer has an acid number of at least 15 wherein the mol ratio of (2) to (3) is between about 1:1 and 1:6, respectively, and wherein the weight ratio of (A) to (B) is between about 95:5 and 60:40.

27. A composition of matter comprising a mixture of (A) a copolymer of (1) methacrylic acid, (2) butyl methacrylate and (3) styrene and (B) triglycidyl cyanurate wherein said copolymer has an acid number of between about 25 and 100, wherein the mol ratio of (2) to (3) is between about 1:2 and 1:4, respectively, and wherein the weight ratio of (A) to (B) is between about :20 and 70:30.

References Cited in the file of this patent UNITED STATES PATENTS 2,604,457 Segall et a1 July 22, 1952 2,604,464 Segall et a1 July 22, 1952 2,741,607 Bradley et al Apr. 10, 1956 

7. A COMPOSITION OF MATER COMPRISING THE REACTION MIXTURE OF (A) A COPOLYMER OF (2) AN ALPHA, BETA ERHYLENICALLY UNSATURATED CARBOXYLIC ACID, (2) AN ALKYL ESTER OF AN ALPHA, BETA ETHYLENICALLY UNSATURATED CARBOXLIC ACID AND (3) A POLYMERIZABLE COMPOUND CONTAINING A CH2=C> GROUP AND DIFFERENT FROM (1) AND (2) WIH (B) THE DEHYDROHALOGENATED REATION PRODUCT OF A MONOHALOHYDRIN OF A SATURATED ALIPHTIC TRIHYDRIC ALCOHOL AND A COMPUND HAVING THE GENERAL FORMULA: 